CN109518162B - Preparation method of bionic mesh-particle structure film material - Google Patents
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Abstract
The invention relates to a preparation method of a bionic mitochondrial structure film material, which comprises the following steps: (1) self-assembling a single layer of micron-scale polystyrene microspheres on a substrate; (2) depositing a layer of TiO on the surface of the polystyrene microsphere by using an atomic layer deposition system2(ii) a (3) In TiO2Carrying out self-assembly of nano-scale multilayer polystyrene spheres on the surface of the coated polystyrene microspheres; (4) electrodeposition of WO in the gap between polystyrene spheres by electrochemical deposition3And calcining to remove the polystyrene to prepare the bionic mesh-particle structure film material. Compared with the prior art, the method is simple in operation method, has universality, can realize preparation of large-area and periodic ordered bionic mesh-particle structure thin film materials, and has wide application potential in the fields of photoelectricity, catalysis, sensing, energy and the like.
Description
Technical Field
The invention relates to the field of bionic materials and application, in particular to a preparation method of a bionic mesh-granular structure film material.
Background
The competitive natural selection principle and the selection mechanism of the advantages and the disadvantages promote the life of the nature to obtain some unique functions in millions of years of evolution. For example, the colorful color of the butterfly wing comes from the micro-nano photonic crystal structure; the sludge of the lotus leaves is not polluted due to thousands of micro-nano hierarchical structures which are arranged in order. The granules are hollow micron-scale particles, and the shell of the particles is provided with a pit structure which is closely arranged, so that the appearance of the granules looks like a football or fullerene. The locusts constantly smear the secreted mitochondria onto the body, and biologists find that an important reason for doing so is that the coating of the mitochondria can form a super-hydrophobic surface, thereby preventing the locusts from being polluted by the viscous excrement secreted by other locusts. Biologists predict that the mitochondria with one of the most complex structures in nature also have excellent light antireflection characteristics, are applied to photoelectric devices, energy and catalysis fields, are beneficial to improving light absorption efficiency, and meanwhile, have hollow porous structures and are beneficial to electron/ion transmission and diffusion. The preparation of the bionic mesh structure is still difficult due to the limitation of material preparation technology.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a bionic mesh structure. The method is suitable for preparing different types of materials, and the structure has an important application prospect in the field of photoelectrocatalysis. The preparation method has universality, simple process and ordered large-area period.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a bionic mitochondrial structure film material comprises the following steps:
(1) self-assembling a single layer of micron-scale polystyrene microspheres on a substrate;
(2) depositing a layer of TiO on the surface of the polystyrene microsphere by using an atomic layer deposition system2；
(3) In TiO2Carrying out self-assembly of nano-scale multilayer polystyrene spheres on the surface of the coated polystyrene microspheres;
(4) electrodeposition of WO in the gap between polystyrene spheres by electrochemical deposition3And calcining to remove the polystyrene to obtain the bionic mesh-particle structure film material.
In the step (1), the substrate is FTO (F-doped SnO)2) Stainless steel or titanium sheet.
The step (1) adopts the following steps: preparing a single-layer microsphere shell by adopting a microsphere self-assembly method, dripping 1-4.5 um polystyrene latex microspheres (2.5 wt% of water dispersion) and 1-2% polystyrene latex microsphere ethanol solution with the concentration of 10% C12H25SO4Drying the silicon chip subjected to hydrophilic treatment by using the Na aqueous solution at 25 ℃ for 1h, assembling the silicon chip on a substrate by a pulling method, and drying the silicon chip in the air at 25 ℃ for 3h for later use.
The step (2) adopts the following steps: depositing TiO on the assembled hexagonal close-packed monolayer small balls2The film has a thickness of 10nm to 30 nm. Placing the single-layer small ball template into an atomic layer deposition device and using TiCl4And H2Depositing TiO by using O as Ti source and O source and inert gas as nitrogen gas in 99.99%2And (3) a layer. Temperature: 80 ℃, pressure: 1X 103～20×103Pa pulse time: 0.1 s-0.3 s, inert gas purging time: 6-18 s, the pulse time of the precursor oxygen source is 0.2-0.3 s, and the inert gas purging time is 6-18 s.The thickness of the film is precisely controlled by the number of ALD cycles, and the film is deposited to obtain TiO2. And carrying out air annealing at 450 ℃ for 2h on the deposited template.
The step (3) adopts the following steps: the upper template is prepared by adopting a template self-assembly method to prepare multilayer polystyrene nanospheres. 200 nm-1000 nm polystyrene latex microspheres (2.5 wt%), 0.1-0.3% aqueous solution, and vertically assembling at 60-80 deg.C for 12-16 h.
The step (4) adopts the following steps: preparation of TiO by electrochemical deposition2/WO3Bionic granular structure, Na with concentration of 16.5%2WO4·2H20.5 ml-1.2 ml of H is added into the O aqueous solution2O2Stirring with constant temperature magnetic stirrer at 20 deg.C for 5 min, adding small amount of isopropanol, and adding HNO3Adjusting the pH to obtain WO3An electrochemical precursor solution. And taking the prepared solution as electrolyte of three electrodes of an electrochemical workstation to carry out electrodeposition. TiO 22The polystyrene ball sample is used as a working electrode, Pt is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. The voltage is-0.5 to-0.2V, the electrodeposition is carried out for 4 to 20min, the drying is carried out for 1h at the temperature of 60 ℃, then the air annealing treatment is carried out, the calcination is carried out for 2 to 3h at the temperature of 500 ℃ at the heating rate of 1 to 5 ℃/min, and the TiO is obtained2/WO3Biomimetic mitochondrial structures.
Compared with the prior art, the invention adopts the atomic layer deposition technology to modify the surface of the polystyrene microsphere and deposits a functional protective layer, thereby being beneficial to the ordered self-assembly of the nano-scale polystyrene microsphere on the surface of the microsphere and simultaneously maintaining the structure of the hollow microsphere after the template is removed by calcination. The surface self-limiting reaction and complementary properties of atomic layer deposition techniques result in the technique having excellent controllability of the thickness and uniformity of the thin film. The structure controls the depth of pits on the surface of the granular structure according to the voltage and time of electrochemical deposition.
Drawings
FIG. 1 is an electron microscope photograph of a close-packed 4.5 μm polystyrene single-layer pellet;
FIG. 2 is TiO2/WO3And (5) scanning electron microscope pictures of the bionic granular structure.
FIG. 3 is TiO2/WO3Biomimetic mitochondrial structure and TiO2/WO3Linear sweep voltammogram (LSV plot) for planar structure contrast.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
A preparation method of a bionic mitochondrial structure film material comprises the following steps:
(1) preparing a single-layer microsphere shell by adopting a microsphere self-assembly method, dripping 1-4.5 um polystyrene latex microspheres (2.5 wt% of water dispersion) and 1-2 wt% polystyrene latex microsphere ethanol solution into 10 wt% of C12H25SO4Drying the silicon wafer subjected to hydrophilic treatment by using an aqueous solution of Na at 25 ℃ for 1h, and assembling the silicon wafer on FTO (F-doped SnO)2) Drying a stainless steel sheet or a titanium sheet substrate for 3 hours at 25 ℃ in the air for self-assembling the single-layer micron-scale polystyrene microspheres on the substrate;
(2) depositing TiO on the assembled hexagonal close-packed monolayer small balls2The film has a thickness of 10nm to 30 nm. Placing the single-layer small ball template into an atomic layer deposition device and using TiCl4And H2Depositing TiO by using O as Ti source and O source and inert gas as nitrogen gas in 99.99%2And (3) a layer. Temperature: 80 ℃, pressure: 1X 103～20×103Pa pulse time: 0.1 s-0.3 s, inert gas purging time: 6-18 s, the pulse time of the precursor oxygen source is 0.2-0.3 s, and the inert gas purging time is 6-18 s. The thickness of the film is precisely controlled by the number of ALD cycles, and the film is deposited to obtain TiO2. Carrying out air annealing at 450 ℃ for 2h on the deposited template;
(3) the upper template is prepared by adopting a template self-assembly method to prepare multilayer polystyrene nanospheres. 200 nm-1000 nm polystyrene latex microspheres (2.5 wt%), 0.1-0.3% aqueous solution, vertically assembling for 12-16 h at 60-80 ℃;
(4) depositing Al on the assembled multilayer nano-scale small balls2O3The film has a thickness of 0.1nm to 0.3 nm. Placing the single-layer small ball template into an atomic layer deposition device, and using Al (CH)3)3And H2Depositing Al by using O as Al source and O source and 99.99% nitrogen as inert gas2O3And (3) a layer. Temperature: 90 ℃, pressure: 1X 103～20×103Pa pulse time: 0.1 s-0.3 s, inert gas purging time: 6-18 s, the pulse time of the precursor oxygen source is 0.2-0.3 s, and the inert gas purging time is 6-18 s. The thickness of the film is accurately controlled by the ALD cycle number, and Al is obtained by deposition2O3；
(5) Preparation of TiO by electrochemical deposition2/WO3Bionic granular structure, Na with concentration of 16.5%2WO4·2H20.5 ml-1.2 ml of H is added into the O aqueous solution2O2Stirring with constant temperature magnetic stirrer at 20 deg.C for 5 min, adding small amount of isopropanol, and adding HNO3Adjusting the pH to obtain WO3An electrochemical precursor solution. And taking the prepared solution as electrolyte of three electrodes of an electrochemical workstation to carry out electrodeposition. TiO 22The polystyrene ball sample is used as a working electrode, Pt is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. The voltage is-0.5 to-0.2V, the electrodeposition is carried out for 4 to 20min, the drying is carried out for 1h at the temperature of 60 ℃, then the air annealing treatment is carried out, the calcination is carried out for 2 to 3h at the temperature of 500 ℃ at the heating rate of 1 to 5 ℃/min, and the TiO is obtained2/WO3Biomimetic mitochondrial structures.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1
TiO2/WO3Of biomimetic mitochondrial structuresPreparation of
The transparent conductive FTO glass is selected as a substrate and is characterized in that the transmittance is as follows: > 80%, sheet resistance: 13 + -1.5 ohm. Putting into a mixed solution (7: 3) of sulfuric acid and hydrogen peroxide for hydrophilic treatment, finally washing with deionized water, and drying with nitrogen.
Selecting polystyrene microspheres with the size of 4.5 mu mm, adding ethanol for dilution according to the proportion of 2:1, and then carrying out ultrasonic treatment to obtain uniform and stable suspoemulsion.
Dropping the microsphere on a hydrophilic silicon wafer, transferring the microsphere to the water surface after drying, and transferring the microsphere to an FTO substrate by a pulling method to form a single-layer polystyrene microsphere membrane as shown in figure 1.
Drying the template in the air, putting the template into atomic layer deposition equipment, and adding TiCl4And H2Depositing 25nm TiO with O as Ti source and O source and 99.99% nitrogen as inert gas2And (3) a layer. Each atomic layer deposition cycle comprises the steps of: the pulse time of the precursor titanium source is 0.1-0.3 s, the inert gas purging time is 6-18 s, the pulse time of the precursor oxygen source is 0.1-0.3 s, and the inert gas purging time is 6-18 s. The thickness of the film was precisely controlled by the number of ALD cycles to yield 25nm TiO2. And carrying out air annealing treatment at 450 ℃ for 2h on the deposited template.
On TiO by vertical deposition2Multilayer polystyrene microsphere self-assembly is carried out on the microsphere template, the size of the polystyrene microsphere is 500nm, the concentration is 0.1%, the deposition temperature is 60 ℃, and the deposition time is 16 h.
Preparation of TiO by electrochemical deposition2/WO3Bionic granular structure, Na with concentration of 16.5%2WO4·2H2Adding 0.5-1.2 ml of H into the O aqueous solution2O2Stirring with constant temperature magnetic stirrer for 5 min, slowly adding small amount of isopropanol, and adding HNO3Adjusting the pH to obtain WO3An electrochemical precursor solution.
And taking the prepared solution as electrolyte of three electrodes of an electrochemical workstation to carry out electrodeposition. TiO 22Polystyrene ball sample as working electrode and Pt as counter currentAnd an Ag/AgCl electrode is used as a reference electrode. Performing electrodeposition at-0.40V for 8min, naturally drying, performing air annealing treatment, and calcining at 500 deg.C for 2h at a heating rate of 1 deg.C/min to obtain TiO2/WO3Biomimetic mitochondrial structures. As shown in fig. 2.
FIG. 3 is TiO2/WO3Biomimetic mitochondrial structure and TiO2/WO3Linear sweep voltammogram (LSV graph) for planar structure contrast, comparing TiO2/WO3Granular structure and planar TiO2/WO3Film structure at 0.5M Na2SO4With 0.1M Na2SO3Middle test of Linear sweep voltammetry Properties, wherein Flat WO3in dark stands for TiO prepared directly on FTO conductive glass2/WO3Photocurrent density of the film in the absence of light, Flat WO3Expressed is TiO directly prepared on FTO conductive glass2/WO3Photocurrent density of the film under light irradiation, Bro WO3in dark stands for TiO prepared on FTO conductive glass2/WO3Photocurrent density of the mitochondrial structure in the absence of light, Bro WO3in dark stands for TiO prepared on FTO conductive glass2/WO3Photocurrent density of the mitochondrial structure in the absence of light. As can be seen from the above curves, ordered hollow porous TiO2/WO3Granular structure, in contrast to planar TiO2/WO3The film has improved photocatalytic performance by 145.59% under the voltage of 1.23V compared with the reversible hydrogen electrode, and shows considerable photocurrent density. The 270-degree ordered pore channels of the structure increase the light absorption in time and space, and the ordered pores form a large specific surface area, so that the contact with the electrolyte is increased, and better electron transmission and separation efficiency is obtained. The multi-light scattering in the air, the size of the pore neck and the formed photonic crystal have good light-capturing effect, so that the structure has better PEC performance.
Example 2
A preparation method of a bionic mitochondrial structure film material comprises the following steps:
(1) preparing a single-layer microsphere shell by adopting a microsphere self-assembly method, dripping 1um polystyrene latex microsphere (2.5 wt% of water dispersion) and 1 wt% polystyrene latex microsphere ethanol solution in 10 wt% of C12H25SO4Drying the silicon chip subjected to hydrophilic treatment by using the Na aqueous solution at 25 ℃ for 1h, then assembling the silicon chip on a stainless steel sheet substrate by using a pulling method, and drying the silicon chip in the air at 25 ℃ for 3h for self-assembling the monolayer micron-scale polystyrene microspheres on the substrate;
(2) depositing TiO on the assembled hexagonal close-packed monolayer small balls2A film with the thickness of 10nm is put into the atomic layer deposition equipment, and TiCl is used for depositing the single-layer small ball template4And H2Depositing TiO by using O as Ti source and O source and inert gas as nitrogen gas in 99.99%2And (3) a layer. Temperature: 80 ℃, pressure: 1X 103Pa pulse time: 0.1s, inert gas purge time: and 6s, the pulse time of the precursor oxygen source is 0.2s, and the inert gas purging time is 6 s. The thickness of the film is precisely controlled by the number of ALD cycles, and the film is deposited to obtain TiO2. Carrying out air annealing at 450 ℃ for 2h on the deposited template;
(3) the upper template is prepared by adopting a template self-assembly method to prepare multilayer polystyrene nanospheres. 200nm polystyrene latex microspheres (2.5 wt%), 0.1 wt% aqueous solution, at 60 deg.C, vertically assembling for 12 h;
(4) depositing Al on the assembled multilayer nano-scale small balls2O3The film thickness is 0.1 nm. Placing the single-layer small ball template into an atomic layer deposition device, and using Al (CH)3)3And H2Depositing Al by using O as Al source and O source and 99.99% nitrogen as inert gas2O3And (3) a layer. Temperature: 90 ℃, pressure: 1X 103Pa pulse time: 0.1s, inert gas purge time: and 6s, the pulse time of the precursor oxygen source is 0.2s, and the inert gas purging time is 6 s. The thickness of the film is accurately controlled by the ALD cycle number, and Al is obtained by deposition2O3；
(5) Preparation of TiO by electrochemical deposition2/WO3Bionic granular structure, Na with concentration of 16.5 wt%2WO4·2H20.5ml of H was added to the O aqueous solution2O2Stirring with constant temperature magnetic stirrer at 20 deg.C for 5 min, adding small amount of isopropanol, and adding HNO3Adjusting the pH to obtain WO3An electrochemical precursor solution. And taking the prepared solution as electrolyte of three electrodes of an electrochemical workstation to carry out electrodeposition. TiO 22The polystyrene ball sample is used as a working electrode, Pt is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. The voltage is-0.5V, the electrodeposition is carried out for 4min, the drying is carried out for 1h at the temperature of 60 ℃, then the air annealing treatment is carried out, the calcination is carried out for 2h at the temperature of 500 ℃ at the heating rate of 1 ℃/min, and the TiO is obtained2/WO3Biomimetic mitochondrial structures.
Example 3
A preparation method of a bionic mitochondrial structure film material comprises the following steps:
(1) preparing a single-layer microsphere shell by adopting a microsphere self-assembly method, dripping a solution of 4.5um polystyrene latex microspheres (2.5 wt% of water dispersion) and 2% polystyrene latex microsphere ethanol solution in the concentration of 10% C12H25SO4Carrying out hydrophilic treatment on a silicon chip by using a Na aqueous solution, drying the silicon chip for 1h at 25 ℃, then assembling the silicon chip on a titanium chip substrate by using a pulling method, and drying the silicon chip for 3h in the air at 25 ℃ for self-assembling the monolayer micron-scale polystyrene microspheres on the substrate;
(2) depositing TiO on the assembled hexagonal close-packed monolayer small balls2The film thickness is 30 nm. Placing the single-layer small ball template into an atomic layer deposition device and using TiCl4And H2Depositing TiO by using O as Ti source and O source and inert gas as nitrogen gas in 99.99%2And (3) a layer. Temperature: 80 ℃, pressure: 20X 103Pa pulse time: 0.3s, inert gas purge time: and 18s, the pulse time of the precursor oxygen source is 0.3s, and the inert gas purging time is 18 s. The thickness of the film is precisely controlled by the number of ALD cycles, and the film is deposited to obtain TiO2. Carrying out air annealing at 450 ℃ for 2h on the deposited template;
(3) the upper template is prepared by adopting a template self-assembly method to prepare multilayer polystyrene nanospheres. 1000nm polystyrene latex microspheres (2.5 wt%), 0.3% aqueous solution, at 80 deg.C, vertically assembling for 16 h;
(4) depositing Al on the assembled multilayer nano-scale small balls2O3The film thickness is 0.3 nm. Placing the single-layer small ball template into an atomic layer deposition device, and using Al (CH)3)3And H2Depositing Al by using O as Al source and O source and 99.99% nitrogen as inert gas2O3And (3) a layer. Temperature: 90 ℃, pressure: 20X 103Pa pulse time: 0.3s, inert gas purge time: and 18s, the pulse time of the precursor oxygen source is 0.3s, and the inert gas purging time is 18 s. The thickness of the film is accurately controlled by the ALD cycle number, and Al is obtained by deposition2O3；
(5) Preparation of TiO by electrochemical deposition2/WO3Bionic granular structure, Na with concentration of 16.5%2WO4·2H21.2ml of H was added to the O aqueous solution2O2Stirring with constant temperature magnetic stirrer at 20 deg.C for 5 min, adding small amount of isopropanol, and adding HNO3Adjusting the pH to obtain WO3An electrochemical precursor solution. And taking the prepared solution as electrolyte of three electrodes of an electrochemical workstation to carry out electrodeposition. TiO 22The polystyrene ball sample is used as a working electrode, Pt is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. Performing electrodeposition at-0.2V for 20min, drying at 60 deg.C for 1h, air annealing, and calcining at 500 deg.C for 3h at a temperature rise rate of 5 deg.C/min to obtain TiO2/WO3Biomimetic mitochondrial structures.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (6)
1. A preparation method of a bionic mitochondrial structure film material is characterized by comprising the following steps:
(1) self-assembling a single layer of micron-scale polystyrene microspheres on a substrate;
(2) depositing a layer of TiO on the surface of the polystyrene microsphere by using an atomic layer deposition system2；
(3) In TiO2Carrying out self-assembly of nano-scale multilayer polystyrene spheres on the surface of the coated polystyrene microspheres; on TiO by vertical deposition2Carrying out self-assembly of multiple layers of polystyrene microspheres on the microsphere template;
(4) electrodeposition of WO in the gap between polystyrene spheres by electrochemical deposition3And calcining to remove the polystyrene to prepare the bionic mesh-particle structure film material.
2. The method for preparing a biomimetic reticulocyte structure membrane material according to claim 1, wherein the substrate in the step (1) is FTO, stainless steel sheet or titanium sheet.
3. The preparation method of the bionic mitochondrial structure film material according to claim 1, characterized in that the step (1) adopts the following steps: preparing a single-layer microsphere shell by adopting a microsphere self-assembly method, dripping 1-4.5 um polystyrene latex microspheres (2.5 wt% of water dispersion) and 1-2 wt% polystyrene latex microsphere ethanol solution into 10 wt% of C12H25SO4Drying the silicon chip subjected to hydrophilic treatment by using the Na aqueous solution at 25 ℃ for 1h, assembling the silicon chip on a substrate by a pulling method, and drying the silicon chip in the air at 25 ℃ for 3h for later use.
4. The method for preparing the bionic mitochondrial structure film material according to claim 1, wherein the step (2) comprises the following steps: depositing TiO on the assembled hexagonal close-packed monolayer small balls2A film with the thickness of 10 nm-30 nm, placing the single-layer micron-scale polystyrene microsphere template into atomic layer deposition equipment, and using TiCl4And H2Depositing TiO by using O as Ti source and O source and inert gas as nitrogen gas in 99.99 v%2A layer of a material selected from the group consisting of,controlling the temperature: 80 ℃, pressure: 1X 103～20×103Pa pulse time: 0.1 s-0.3 s, inert gas purging time: 6-18 s, the pulse time of the precursor oxygen source is 0.2-0.3 s, the inert gas purging time is 6-18 s, the thickness of the film is accurately controlled through the ALD cycle number, and TiO is obtained through deposition2And carrying out air annealing at 450 ℃ for 2h on the deposited template.
5. The method for preparing the bionic mitochondrial structure film material according to claim 1, wherein the step (3) comprises the following steps: preparing an upper template by adopting a template self-assembly method to prepare multilayer polystyrene nanospheres, and vertically assembling 200-1000 nm polystyrene latex microspheres (2.5 wt%) and 0.1-0.3 wt% aqueous solution at the temperature of 60-80 ℃ for 12-16 h.
6. The method for preparing the bionic mitochondrial structure film material according to claim 1, wherein the step (4) comprises the following steps: preparation of TiO by electrochemical deposition2/WO3Bionic granular structure, Na with concentration of 16.5 wt%2WO4·2H2Adding H into O aqueous solution2O2Stirring with constant temperature magnetic stirrer at 20 deg.C for 5 min, adding small amount of isopropanol, and adding HNO3Adjusting the pH to obtain WO3An electrochemical precursor solution;
the prepared solution is used as electrolyte of three electrodes of an electrochemical workstation for electrodeposition, and TiO is added2Taking a polystyrene ball sample as a working electrode, Pt as a counter electrode, an Ag/AgCl electrode as a reference electrode, carrying out electrodeposition for 4-20 min at a voltage of-0.5 to-0.2V, drying at 60 ℃ for 1h, then carrying out air annealing treatment, calcining at 500 ℃ for 2-3 h at a heating rate of 1-5 ℃/min to obtain TiO2/WO3Biomimetic mitochondrial structures.
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